Process for preparation of derivatives of phosphinous acid

ABSTRACT

New chemical product, constituted by an organic phosphorus compound of the structure ##STR1## where Q is an N or O atom, T is an alkylene or arylene, possibly carrying substituents, or not existing, while R 1  to R 7 , the same or different, are H or aliphatic, cycloaliphatic and/or arylic hydrocarbon radicals, possibly substituted, R 3  not existing when Q is oxygen. This product is used as an intermediate in the preparation of different derivatives of phosphinous acid.

This is a division of application Ser. No. 07/538,010, filed Jun. 14,1990, abandoned, which is a division of application Ser. No. 07/089,592,filed Aug. 26, 1987 and now U.S. Pat. No. 4,952,728.

The invention relates to a process for preparation of derivatives ofphosphinous acid. It opens a new way of easy access to phosphinites,phosphines, phosphine oxides, diphosphinites, diphosphines, phosphinedioxides and similar products, by reactions known in themselves,starting from new intermediates according to the present invention. Thelatter also comprises a process for obtaining these intermediatecompounds.

The various compounds named above, derivatives of phosphinous acid, havediverse industrial applications: they serve in the synthesis of variousorganic phosphorus compounds and are used in the preparation ofoptically active catalysts comprising optically active organophosphorusligands. Some phosphines find advantageous application in catalyticsystems, for example for the production of mercaptans starting fromolefins and H₂ S. Phosphines are also employed in the preparation ofcatalysts based on metals: notably for the polymerisation of olefinswith the aid of Ni complexes with phosphines, or isomerisation ofunsaturated hydrocarbons with complexes of compounds of Ru andphosphines.

Given the interest which different derivatives of phosphinous acid thuspresent, it was important to research economic means for theirsynthesis, in particular their asymmetric synthesis. The presentinvention responds to this need; it allows the derivatives in questionto be obtained in a smaller number of operations than were involved inprior processes. It is possible, thanks to the invention, to obtainoptically active compounds, whilst recovering the asymmetric inductorintact.

The intermediate compounds, as well as the derivatives of phosphinousacid, can be in the form of complexes, which generally provide theadvantage of an improved stability and lower susceptibility tooxidation.

The intermediate compounds, according to the invention are organiccompounds of phosphorus characterised by the structure: ##STR2## where Qis an N or O atom, T is an alkylene or arylene, possibly carryingsubstituents, or not existing, while R¹ to R⁷, the same or different,are H or aliphatic, cycloaliphatic and/or arylic hydrocarbon radicals,R³ not existing when Q is oxygen. More particularly, the R¹ to R⁷ can beC₁ to C₁₈ alkyls or alkenyls, especially C₁ to C₆, or phenyls possiblycarrying one or more C₁ to C₆ alkyl substituents. This signifies thatcertain of the R¹ to R⁷ groups can be aryls, and others alkyls,cycloalkyls or alkenyls, possibly substituted.

In particular R¹ can be methyl, ethyl, propyl or butyl, R² being phenyl,or vice-versa.

These compounds can exist and be used in the form of complexes with thephosphorus atom bonded to a metal compound M: ##STR3## The metalcomplexants can be, for example, different carbonyls of transitionmetals, in particular W(CO)₅ or Mo(CO)₅, metal halogens such as CuBr,hydrides, notably BH₃, etc.

Moreover, the invention comprises the di-compounds of the formula (1),which can be represented by the formula (2) below: ##STR4## where R¹ isa divalent hydrocarbon radical, particularl an alkylene, cycloalkyleneor arylene.

As in the case of the mono-compounds, the di-compounds of the formula(2) can be complexed on one or both of the P atoms.

When Q is a nitrogen atom, the intermediate compounds according to theinvention are hydroxy monoaminophosphines and dihydroxy di-(aminophosphines) ##STR5##

When Q is an oxygen atom, these compounds are respectively phosphinitesand diphosphinites of the hydrocarbon radical --CR⁴ R⁶ --T--CR⁵ R⁷ --OH,which carries an hydroxyl at the end of the chain.

Some of these intermediate compounds are described, by way of examples,below, after the description of a process for their preparation.

The intermediate products, according to the invention are prepared by aprocess characterised in that an organometallic compound is reacted withan oxazaphosphacycloalkane, a di-oxazaphosphacycloalkane, adioxaphosphacycloalkane or a bisdioxaphosphacycloalkane, and theorganometallic salt formed is then hydrolysed.

Put otherwise, a preparation according to the following scheme iscarried out: ##STR6## or, in analogous fashion, starting from adi-compound: ##STR7##

Common organometallic compounds, such as compounds of magnesium,aluminium, zinc etc. and, most particularly, organolithium compounds,notably aryl lithium compounds and alkyl lithium compounds with C₁ toC₁₂ alkyls are suitable for the carrying out of the invention. R¹¹ isalkylene or arylene.

The reaction can take place with an oxa-compound as starting materialcomplexed on the phosphorus, to give intermediate complexes, asindicated above, with reference to compound (1).

Beginning with intermediates (1) and (2), it is easy to go economicallyto different phosphinous acid derivatives, of industrial interest, ingeneral by reactions known in themselves.

Thus one can, starting with a hydroxylated aminophosphine (3), reach aphosphinite by alcoholysis: ##STR8## and the phosphinite can beconverted to phosphine ##STR9## by the action of an R⁹ aryl or alkylorganometallic compound, in particular of Mg or Li. This allowsoptically active trialkyl-, dialkyl-, aryl-, aryldialkyl- and triaryl-phosphines to be obtained with good yields.

Another application of the intermediate product (3) is in the synthesisof a phosphine oxide, by the action of an alkyl halide on theaminophosphine (3): ##STR10##

One such reaction took place with good yield and allowed the phosphineoxide with an optical purity of 40-100% to be obtained.

Also, a halogenophosphine ##STR11## can be obtained by the action of ahydrohalic acid HX on the compound (3). The phosphinous acid itself canbe produced by hydrolysis of the compound (3).

Such compounds, except the phosphine oxide, can be obtained in thecomplexed form, by the same reactions applied to a complex ##STR12##where M represents a complexing metal group, in particular W(CO)₅,Mo(CO)₅ or BH₃.

In analogous manner one can obtain a diphosphinite, a phosphine dioxide,a dihalogenophosphine or a phosphinous diacid by, respectively, thealcoholysis, action of an alkyl halide, action of a hydrohalic acid, orhydrolysis of a di-hydroxyaminophosphine (4) mentioned above.

As shown in relation to reaction (5), an intermediate product accordingto the invention can be prepared by the action of an organometalliccompound and hydrolysis on a cyclic phosphorus compound of which thering comprises (as Q) a nitrogen or oxygen atom. When Q is 0, the cyclicstarting material compound (5) is a dioxaphosphacycloalkane ##STR13##which, after reaction with an organometallic compound R² M andsubsequent hydrolysis, gives a phosphinite ##STR14## In the same mannera bis-dioxaphosphacycloalkane according to formula (6) gives adiphosphinite analagous to compound (2).

This manner of preparation of intermediate compounds, according to theinvention, is particularly practical and economical, since the startingmaterial, that it is to say the dioxaphosphacycloalkanes and thebis-dioxaphosphacycloalkanes, are easily obtained, particularly bycondensation of commercial dichlorophosphine with a corresponding diol.They lead regio- and stereo-specifically to phosphinites (7).

As aminophosphines (3), the hydroxylphosphinites (7) permit synthesis ofvarious derivatives of phosphinous acid, in particular asymmetricsynthesis thereof. Thus, phosphine oxides are produced by reaction withalkyl halides; phosphines by the action of an organometallic compound,possibly complexed, for example CuBr, W(CO)₅ or BH₃.

It is noted that, after having used a commercial symmetric phosphine,such as a dichlorophosphine, for the preparation of thedioxaphosphacycloalkane starting material, one can obtainstereo-selectively, according to reaction (5) and a second treatmentwith an organometallic compound, a new asymmetric phosphine. To do so,the following is carried out after the first operation (5): ##STR15##

It is also to be observed that, within the framework of the invention,it possible to use asymmetric inductors, easily accessible at littlecost, such as chloramphenicol, the derivatives of ethyl lactate or thecamphoquinone.

On the other hand, as will be seen, a phosphine can be prepared in onlythree steps starting from a diol, the latter two steps, that is to saythe reactions (5) and (8), being capable of being carried out in thesame solvent medium, the one after the other. Besides, the phosphine canbe complexed in that same medium, to give a stable, easily storedcompound.

All the reactions which produce phosphinites (7) can also be carried outin analagous manner with diphosphinites ##STR16##

The invention is illustrated by the non-limiting examples which follow:

EXAMPLE 1

Preparation of N-methyl N-(1-hydroxy 1-phenyl 2-propyl) methyl phenylaminophosphine (Sp, 1R, 2S) ##STR17## that is to say the compound offormula (3), given above, in which R¹ and R⁴ are methyls and R² and R⁵phenyls, R⁶ and R⁷ being hydrogen atoms, whilst T is only a simple bond.

The preparation is carried out according to reaction (5) in thefollowing manner.

In a 100 ml flask, fitted with a stirrer, 1 mmole (271 mg) ofoxazaphospholidine ##STR18## is dissolved in 5 ml of THF. To the cooledmixture, placed under an inert atmosphere, particularly argon, 1 ml ofLiCH₃, that is to say 625 μl of a 1.6M solution of methyl lithium isadded. After 15 minutes of stirring, 1 mmole of water is added toneutralise the reaction mixture, then the temperature is brought back to25° C. ³¹ P NMR analysis (20%.C₆ D₆.THF) indicates the quantitativeformation of the aminophosphine (10) δ³¹ P=-26.4 ppm). The structure(10) is confirmed by the formation of a tungsten compound (10') of type(3') with W(CO)₅ THF by the usual method, that is to say the irradiationfor 1/2 h of W(CO)₆ in THF, after the addition of aminophosphine (10).Purification by chromotography on silica; obtained 410 mg; yield 67%.The characteristics of the complex (10'), not crystallised, follow:

δ³¹ P=+64 ppm (CDCl₃); J_(PW) =261 Hz

    ______________________________________                                        .sup.1 H NMR (CDCl.sub.3)                                                     ______________________________________                                        doublet (3H)        1,2 ppm        J=7Hz                                      doublet (3H)        1,8 ppm        J.sub.PH =5Hz                              doublet (3H)        2,6 ppm                                                   multiplet (1H)      3,8 ppm                                                   doublet (1H)        4,6 ppm        J.sub.HH =8Hz                              massif (10H)        6,8-7,6 ppm                                               ______________________________________                                        Analysis C.sub.22 H.sub.22 NO.sub.6 PW                                                    % C          % H    % N                                           ______________________________________                                        Calculated: 43,21        3,6    2,29                                          Found:      43,00        3,36   2,55                                          ______________________________________                                    

IR (net): ν_(OH) =3400 cm⁻¹ ; ν_(CO) =2080 cm⁻¹, 1926 cm⁻¹, 1980 cm⁻¹

Mass: (W=184); M.sup..+ -28=583; rotatory power: [α]_(D) ¹⁹ =+7,03 (c=7.CH₂ Cl₂)

The compounds (10) and (10') are novel and illustrate by their examplethe action of an alkyl lithium according to the reaction scheme (5).

EXAMPLE 2

Preparation of a diastereomer of compound (10) of example 1, namely ofN-methyl N-(1-hydroxy 1-phenyl 2-propyl) methyl phenyl aminophosphine(R_(p),1R,2S) ##STR19##

According to a method similar to that of example 1, 1 mmole of phenyllithium, that is to say 1 ml of a 1M solution is added to 1 mmole (209mg) of oxazaphospholidine (5") ##STR20## After 30 min at -78° C., thereaction mixture is hydrolysed with 40 μl of H₂ O. ³¹ P NMR analysisindicates the formation of compound (11): δ³¹ P=-26 ppm, C₆ D₆ +THF. Thestructure (11) is confirmed by complexation with W(CO)₅ THF, which leadsto compound (11'), a diastereomer of (10'), purified by chromotographyon silica (eluant hexane--AcOEt 10%);--obtained 310 mg--yield 50%.

Characteristic of compound (11'), that is to say of (11) carrying thecomplexing group W(CO)₅ on the P atom: ##STR21##

δ³¹ P=+64,1 ppm; Jpw=260 Hz

mass: (W=184)M.sup..± 28=583

    ______________________________________                                        .sup.1 H NMR (CDCl.sub.3)                                                     ______________________________________                                        doublet (3H)        1,25 ppm       J=7Hz                                      doublet (3H)        2,05 ppm       J.sub.PH =5Hz                              doublet (3H)        2,55 ppm                                                  multiplet (1H)      3,8 ppm                                                   doublet (1H)        4,6 ppm        J.sub.HH =9Hz                              massif (10H)        6,8-7,6 ppm                                               ______________________________________                                    

IR(net): ν_(OH) =3400 cm⁻¹ ν_(C)═O =2080 cm⁻¹, 1980 cm⁻¹, 1925 cm⁻¹

The compounds (11) and (11') are novel and illustrate by way of examplethe addition of an aryl lithium according to the invention.

EXAMPLE 3

Preparation of N-methyl N-(1-hydroxy 1-phenyl 2-propyl) butyl phenylaminophosphine (5p, 1R, 2S). According to a method similar to that ofexample 1, 1 mmole of butyl lithium is added to 271 mg ofoxazaphospholidine (5') (R¹ =Ph). After 2 hours of reaction at atemperature between -78° and -40° C. (³¹ P NMR δ=-26.4 ppm), theaminophosphine product was recovered.

EXAMPLE 4

Preparation of a complexed aminophosphine (3') starting with anoxazaphospholidine carrying the complexing group W(CO)₅ on thephosphorus ##STR22## by the action of CH₃ Li on the compound (12).

In a 100 ml flask, 595 mg of complex (12) (˜1 mmole) are dissolved in 5ml of anhydrous THF and placed in an inert atmosphere (Ar) at -78° C.After addition of 1 mmole of methyl lithium, the mixture is left underthese conditions for 6 hours, then it is neutralised with 40 μl of waterand dried on Na₂ SO₄. The evaporation of solvent gives a residue whichis chromatographed on silica (eluant: AcOEt 5%, hexane 95%); obtained470 mg; yield 77%.

The compound obtained has the same characteristics as the complex (10')prepared according to example 1.

It is to be noted that the compounds are more stable, as well as lesssubject to oxidation, in their complexed forms.

By analagous operations, but starting from the oxazaphospholidine (5')complexed on P of example 2, and replacing CH₃ Li by C₆ H₅ Li, oneobtains the complexed aminophosphine (11') comprising the group##STR23## the characteristics of which are given in example 2.

EXAMPLE 5

Preparation of an intermediate product (7) starting fromdioxaphosphacycloalkane.

The reaction (5) is applied to a dioxaphosphacycloalkane, that is to saythe dioxaphospholane (Q=0) ##STR24## which is reacted with butyllithium.

In a 100 ml flask, fitted with a stirrer, 334 mg (1 mmole) ofdioxaphospholane are dissolved in 5 ml of THF in an atmosphere of argon.To the mixture coiled to -78° C. 1 mmole of butyl lithium, that is 500μl of 2M solution, is added. After 10 min of stirring the ³¹ P NMRanalysis of the mixture (20% C₆ D₆ of THF) indicates the quantitativeformation of phosphinite (δ³¹ P=-26.5 ppm) ##STR25## that is to say, of1,1-diphenyl, 2-hydroxypropyl butyl phenyl phosphinite (Rp, 2S).

This compound is novel. Its formation is confirmed by its reaction withthe equivalent of CH₃ Li at -78° C., directly in the reaction mixture ofits preparation, then stopping of the reaction by the addition of H₂ Oone obtains, with a yield of 61%, the phosphine ##STR26## which has thefollowing characteristics.

³¹ P NMR δ=-37 ppm (20% C₆ D₆ - THF)

¹ H NMR: massif: 0.65-1.78 ppm (9H); doublet: 1.5 ppm (3H); J_(PH) =15Hz; massif: 7-7.8 ppm (5H)

EXAMPLE 6

Preparation of a substituted intermediate (7) derived fromchloramphenicol, starting from a special dioxaphosphorinane (14).

The compound (14) is the phosphinite (-) 5-dichloroacetamido 4-(4-nitrophenyl) 2-phenyl-1,3,2,dioxaphosphrinane (2R, 4R,5R) ##STR27## thepreparation of which is described in French Patent 2 562 543, on page 8.

The method of the reaction of compound (14) with the o-anisyl lithium##STR28## is the same as in example 5, except that three equivalents ofo-anisyl lithium, in place of butyl lithium, are added to 429 mg ofdioxaphosphorinane (14)

The novel product, obtained after 4 hours at -78°→-40° C., is theo-anisyl phenyl phosphinite ##STR29##

EXAMPLE 7

Application of complexed intermediate compound (10') in the productionof a halogenophosphine (16).

The complex (10'), described in example 1, is treated by gaseous HCl insolution in dichloromethane, to give the reaction: ##STR30##

Into a 100 ml flask, 95 mg of complexed aminophosphine (10') dissolvedin 10 ml of CH₂ Cl₂ were introduced. After bubbling dry HCl gas for 30min, the CCM indicated the disappearance of starting material. Milliporefiltration of the reaction mixture, followed by evaporation of thesolvent, gave 70 mg of compound (16) with a yield of 93%. Theprecipitate, formed in the course of the reaction, turned out to be thechlorohydrate of ephedrine ([α]_(D) =-34.6°).

Characteristics of compound (16):

³¹ P NMR (CDCl₃): δ=+103,6 ppm; Jpw=290 Hz

¹ H NMR (CDCl₃): doublet: (3H) 2,57 ppm, J_(PH) =5Hz; massif: (5H) 7,4-8ppm

Mass: (w=184); (EI; 70 eV); M.sup..+ =482; peak of base 342 (M.sup..+-140)

IR (KBr): ν_(co) =2065, 1930 cm⁻¹

EXAMPLE 8

Application of an intermediate product (10') in the preparation of aphosphinous acid, the complexes being more stable and less oxidisiblethan the phosphinous compounds themselves, here the complexed compound(10') of example 7 was again used. The decomplexation took place easily,in the known manner, not needing to be described.

The complexed phosphinous acid is obtained by acid hydrolysis startingfrom the aminophosphine (10') ##STR31## For this, in a 100 ml flask,fitted with an upright condenser, 1 mmole of complexed aminophosphine(611 mg) is heated for 1 hour at 65° C. in 10 ml of a 5M mixture ofacetonitrile and sulphuric acid CH₃ CH/H₂ SO₄ (10:1). After cooling, themixture is neutralised by NaHCO₃ in saturated acqueous solution, thenextracted with CH₂ Cl₂. Drying, then evaporation of the organic phase,gives a residue which is chromatographed on silica to separate (AcOEt10% - Hexane - rf 0.4-) the compound (17) obtained 45 mg, yield 97%[δ]_(D) =+4.8° (c=3 CH₂ Cl₂).

not cristallised

³¹ P NMR (CDCl₃); δ=+102,9 ppm; J_(pw) =264 Hz

¹ H NMR (COCl₃): doublet: (3H) 2,12 ppm; J_(PH) =6Hz large singlet: (1H)4,6 ppm massif: (5H) 7,3-7,6 ppm

IR: (net): ν_(OH) 3600 cm⁻¹, 2700 cm⁻¹ ; ν_(C) =O 2080 CM⁻¹, 1925 cm⁻¹

Mass: W=184, (EI, 70eV), M'⁺ =464, M'⁺ -140=324 (peak of base)

EXAMPLE 9

Application of complexed intermediate compound (10') in the preparationof an alkyl phosphinite.

The tungsten complex, the aminophosphine (10') obtained according toexample 1, is subjected to the methanolysis which gives: ##STR32##

In a 100 ml flask, fitted with a stirrer, 560 mg, that is to say 0.92mol, of complexed aminophosphine (10') are dissolved in 5 ml of 5Mmethanol/H₂ SO₄. After 3 hours at ambient temperature, the mixture isneutralised by a saturated solution of NaHCO₃ and extracted with CH₂Cl₂. Drying and evaporation of the organic phase gives 380 mg of aresidue which turned out to be 4:1 mixture of products (17) and (18)(yield 80%), which were separated by chromotography on silica (AcOEt10% - Hexane).

The rotatory power of the phosphinous ester (18) obtained is [α]_(D)=+1.2° (c=1.2 CH₂ Cl₂).

In replacing methanol by isopropanol in the above preparation, thehomologeous isopropyl ester of product (17) was obtained in two hours at68° C.

EXAMPLE 10

Application of an intermediate product of the type (7), in particular(13), in the production of a phosphine.

The compound (13) of example (5) is treated by an organometalliccompound, particularly by an alkyl or aryl lithium, then the reactionmedium is stopped by the addition of a small quantity of water.

1 equivalent of CH₃ Li is added to 1 mmole of compound (13) in solutionin THF and the mixture is maintained at -78° C. for 10 min. After coldevaporation of solvent, the residue is recovered in hexane and themineral salts are separated by filtration. A further evaporation gives,with a yield of 61%, 140 mg.

An advantage of the invention is that this operation can be easilycarried out in the same reaction medium in which the intermediatecompound has been prepared (see example 5).

One can thus carry out in two steps in the same solvent: ##STR33##

After separation of this latter product, it can be converted into aphosphine oxide, for example by treatment with H₂ O₂.

EXAMPLE 11

Application of intermediate compound (15) in the preparation of aphosphine.

o-anisyl phenyl phosphinite (15) of example 6 is heated at 60° C. for 3hours with a stoichiometric quantity of CH₃ I in solution in THF. Theevaporation of solvent leaves a residue which is chromatographed onsilica (acetone).

The product obtained is the oxide of o-anisyl methyl phenyl phosphine##STR34## identified by the following characteristics:

[α]_(D) ²⁰ =-11,97° (c=2 CH₃ OH)

    ______________________________________                                        .sup.1 H NMR                                                                  ______________________________________                                        doublet    2,05 ppm  (3H)       J.sub.PH =15Hz                                singlet    3,7 ppm   (3H)                                                     massif     6,8-8,1 ppm                                                                             (3H)                                                     ______________________________________                                    

As mentioned above, R¹ can be, in particular, methyl, ethyl, propyl orbutyl, R² being phenyl or vice-versa.

EXAMPLE 12

Preparation of N-methyl N-(1-hydroxy 1-phenyl 2-propyl) o-anisyl phenylphosphine (R_(p) ; 1R, 2S) ##STR35##

This is the compound of formula (3) given above, in which R¹ iso-anisyl, R² and R⁵ phenyls, R³ and R⁴ methyls, R⁶ and R⁷ hydrogenatoms, while T is only a simple bond. The compound 19 is novel. Thepreparation is carried out according to a method similar to that ofexample 1, by replacing methyl lithium by o-anisyl lithium. The durationof reaction is then 3 hours, and the temperature increased graduallyfrom -78° to -20° C. The aminophosphine is not isolated, but trappedwith two equivalents of methyl iodide to give the oxide of o-anisylmethyl phenyl phosphine described in example 11. Here the reaction##STR36##

EXAMPLE 13

Preparation of a phosphinite intermediate product (7) starting from adioxaphosphacycloalkane obtained by condensation of (2-methoxy phenyl)dichloro phosphine with the (-) 1,1-diphenyl propan-1,2-diol (2S) (20)##STR37## which is a new compound. According to the method described inexample 5, 1 mmol of dioxaphospholane (20) is reacted with 1 equivalentof methyl lithium in 10 ml of THF at -78° C. After 5 mins of stirring,³¹ P NMR analysis indicates δ³¹ P=26 ppm which is characteristic ofphosphinite (21) ##STR38## The 1,1-diphenyl, 2-hydroxy propyl o-anisylmethyl phosphinite (R_(p), 2S) is a new compound. Its formation isconfirmed by the addition of an equivalent of phenyl lithium. After halfan hour, the mixture is hydrolysed and evaporated to dryness (weightobtained 33 mg). ¹ H NMR analysis indicates a mixture of o-anisyl methylphenyl phosphine and some 1,1-diphenyl propan-1,2-diol. Yield ofphosphine: 50%.

Clear yellow oil

    ______________________________________                                        .sup.1 H NMR o-anisyl methyl phenyl phosphine                                 (CDCl.sub.3)                                                                  ______________________________________                                        doublet    (3H)   J.sub.HP   4Hz  1.63 ppm                                    singlet    (3H)                   3.85 ppm                                    massif     (9H)                   7.79 ppm                                    ______________________________________                                    

The addition of 5 ml of 20% H₂ O₂ to the medium effected thetransformation to phosphine oxide. After washing with water andextraction with dichloromethane, the organic phase is evaporated and theresidue is chromatographed on silica (eluant acetone - rf 0.5). Thephosphine oxide is obtained with a yield of 50%. [α]_(D) =-5.1° (20 ee)

EXAMPLE 14

Application of the complexed phosphinous acid complex (17) is thepreparation of methyl phosphinite (18).

The tungsten complex (17) ([α]_(D) =17° pF=115°) was obtained accordingto the method described in example 9 (5M isopropanol/H₂ SO₄). 100 mg ofcomplex (17) was disolved in 10 ml of an ether solution of diazomethane0.4M at 0° C. After four hours of stirring, the solution is evaporatedand chromatographed on silica: 10% AcOEt/Hexane (rf 0.8). Thephosphinite (18) is obtained with a 60% yield (63 mg).

[α]_(D) =+1.46° (c=1 CH₂ Cl₂)

    ______________________________________                                        .sup.1 H NMR (CDCl.sub.3)                                                     ______________________________________                                        doublet  (3H)       2.15 ppm      J.sub.PH =6H.sub.z                           "       (3H)       3.5 ppm       J.sub.POCH =12H.sub.z                       massif   (5H)       7.5-7.8 ppm                                               ______________________________________                                    

EXAMPLE 15

Preparation of a phosphinite intermediate (23) complexed to a W(CO)₅group ##STR39## The complexed phosphinite (23) corresponds to theformula (7) in which R¹, R⁴ and R⁶ are phenyls, R² and R⁵ methyls, R⁷ ahydrogen and T a bond. The atom of phosphorus is held in thecoordination sphere of tungsten (W(CO)₅). This novel compound isobtained by the action of methyl lithium on the phosphonite complex (22)(-78° C.; THF; 2 h; yield 60%). The product (23) is purified bychromatography on silica (15% AcOEt/Hexane:rf:0.3).

Oil

    ______________________________________                                        .sup.1 H NMR (CDCl.sub.3)                                                     ______________________________________                                        doublet  (3H)        1.15 ppm      J.sub.HH =7Hz                               "       "           2 ppm         J.sub.PH =4Hz                              multiplet                                                                              (1H)        5.1 ppm                                                  singlet  (1H)        2.9 ppm                                                  massif   (15H)       7-7.8 ppm                                                ______________________________________                                    

[α]_(D) =11° (C=2 CHCl₃)

The precursor complex (22) is a novel compound prepared according to aconventional method, that is to say irradiation 1/2 h of W(CO)₆ in THF,then addition of dioxaphospholane obtained by reaction ofdichlorophenylphosphine with the (-) 1,1-diphenyl propan-1,2-diol. Thepurification of this complex (22) is carried out by chromatography onsilica (eluant: 10% AcOEt/Hexane - rf 0.6).

PF=150° C.

[α]_(D) =-85° (C=3.6 CHCl₃)

    ______________________________________                                        .sup.1 H NMR (CDCl.sub.3)                                                     ______________________________________                                        doublet (3H)   1.15 ppm        J=8Hz                                          double quadruplet                                                                            4.85 ppm        (J.sub.HH =8Hz (1H)                                                           (J.sub.POCH =2Hz                               massif (15H)   7-7.8 ppm                                                      ______________________________________                                    

We claim:
 1. A phosphinite of the formula ##STR40## the groups R¹, R²,R⁴, R⁵, R⁶ and R⁷ are individually selected from the group consisting ofhydrogen and 1 to 18 carbon atom alkyl, alkenyl, cycloalkyl and phenylgroups, T is alkylene, arylene or a bond and R¹¹ is a 1 to 18 carbonatom alkylene, alkenylene, cycloalkylene or phenylene group.
 2. Thephosphinite of claim 1 in which T is a bond and the organic grouprepresented by R¹, R², R⁴, R⁵, R⁶ and R⁷ contain 1 to 8 carbon atoms. 3.The phosphinite of claim 2 in which the organic groups represented byR¹, R², R⁴, R⁵, R⁶ and R⁷ contain 1 to 6 carbon atoms.
 4. Thephosphinite of claim 3 in which R¹, R², R⁴, R⁵, R⁶ and R⁷ areindividually selected from the group consisting of hydrogen, alkyl,alkenyl and phenyl groups and R¹¹ is alkylene, alkenylene or phenylene.5. The phosphinite of claim 1 of formula II.
 6. The phosphinite of claim1 of formula I in which said compound is optically active.
 7. Thephosphinite of claim 1 of formula I in which R¹ phenyl and R⁷ ishydrogen.
 8. The phosphinite of claim 7 in which T is a bond, R² and R⁵are methyl and R⁴ is phenyl.
 9. The phosphinite of claim 7 in which R²is butyl, R⁵ is methyl and R⁴ and R⁶ are phenyl.
 10. A method for thepreparation of the phosphinite of claim 1 which comprises reacting acompound of the formula ##STR41## or said compound in the form of acomplex with a metal compound bonded to at least one of the phosphorusatoms therein with an organometallic compound including R₂ andhydrolyzing the organometallic salt thus produced.
 11. The method ofclaim 10 in which the organometallic compound is a compound ofmagnesium, aluminum or zinc.
 12. The method of claim 10 in which theorganometallic compound is an aryl or alkyl lithium.
 13. The method ofclaim 10 in which R¹, R², R⁴, R⁵, R⁶ and R⁷ are individually selectedfrom the group consisting of hydrogen, alkyl, alkenyl and phenyl groupsand R¹¹ is alkylene, alkenylene or phenylene.
 14. The method of claim 10in which the compound of said formula is optically active.
 15. Themethod of claim 10 in which said compound is of formula I'.
 16. Themethod of claim 15 in which R¹, R⁵, and R⁷ are phenyl, R⁴ is hydrogen,R⁶ is methyl, T is a bond and the organometallic compound is butyllithium.
 17. The method of claim 15 in which R¹ is methoxyphenyl, R⁴ ishydrogen, R⁵ and R⁷ are phenyl, R⁶ is methyl and the organometallic saltis methyl lithium.
 18. The method of claim 15 in which R¹, R⁵, and R⁷are phenyl, R⁴ is hydrogen, R⁶ is methyl, T is a bond and the phosphorusatom is complexed with tungsten carbonyl and the organometallic compoundis methyl lithium.